CN105742677B - Nafion/ phosphorylation graphene oxide hybridized film and preparation and application - Google Patents
Nafion/ phosphorylation graphene oxide hybridized film and preparation and application Download PDFInfo
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- CN105742677B CN105742677B CN201610098921.5A CN201610098921A CN105742677B CN 105742677 B CN105742677 B CN 105742677B CN 201610098921 A CN201610098921 A CN 201610098921A CN 105742677 B CN105742677 B CN 105742677B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a kind of Nafion/ phosphorylation graphene oxide hybridized films, are made of Nafion and phosphorylation graphene oxide, with a thickness of 40~70 μm, wherein phosphorylation graphene oxide is 0.005~0.02:1 with Nafion mass ratio.Its preparation process includes: that Hummers method prepares graphene oxide；It is reacted by dopamine with carboxyl on graphene oxide, the amine-modified graphene oxide of DOPA is prepared, then by the Michael addition reaction between dopamine and alendronic acid, to prepare phosphorylation graphene oxide；Phosphorylation graphene oxide is blended to obtain casting solution with Nafion solution, prolongs to flow on clean glass plate and forms a film, and the hybridized film is made.Operation is simple for the preparation process of hybridized film of the present invention, environmentally protective, and Nafion/ phosphorylation graphene oxide hybridized film obtained is applied to Proton Exchange Membrane Fuel Cells, there is higher proton conductivity under 100% humidity and low humidity.
Description
Technical field
The present invention relates to Nafion/ phosphorylation graphene oxide hybridized film and preparations and application, belong to proton exchange membrane combustion
Expect battery technology field.
Background technique
Fuel cell be it is a kind of with renewable resource (such as hydrogen, methanol) for fuel, directly will without combustion process
Its chemical energy is converted into the electrochemical appliance of electric energy.Compared with traditional energy, fuel cell has energy density height, environment friend
Well, the advantages that raw material sources are wide, thus become the another new-generation skill after the conventional power generations technology such as thermoelectricity, water power, nuclear power
Art.Wherein, Proton Exchange Membrane Fuel Cells (Proton exchange membrane fuel cell, PEMFC) has energy
The unique advantages such as high conversion rate, specific power are big, starting speed is fast at room temperature, structure is simple, in stationary power generation and portable electric
Source domain is widely applied.Proton exchange membrane is one of core component of Proton Exchange Membrane Fuel Cells, plays barrier combustion
The effect of material, proton conducting, directly determines the quality of fuel battery performance.Ideal proton exchange membrane is good in addition to that should have
Mechanical performance, outside swelling resistance, should also there is higher proton conductivity, and be still able to maintain under high temperature low humidity excellent
Proton conductivity.
In current commercialized proton exchange membrane, the Nafion membrane of DoPont company production is Typical Representative, it is by hydrophobic
Property the hydrophilic side-chains of polytetrafluoroethylene (PTFE) main chain and end with sulfonate radical form, have good thermal stability, chemistry steady
Qualitative, close and distant pool occurs microphase-separated and forms continuous proton transfer channel so that Nafion membrane have at room temperature it is higher
Proton conductivity.But the problems such as there is also proton conductivities under high temperature low humidity sharply to decline, fuel infiltration is serious, system
About it is further applied.
In recent years, graphene oxide has obtained extensive research in Proton Exchange Membrane Fuel Cells field.Graphene oxide tool
There are good hydrophily, large specific surface area, and surface easily to modify other active groups, increase proton transfer site, solely
Special two-dimensional sheet structure is the ideal carrier of proton conduction, can construct out continuous proton transfer channel, promotes proton conduction
The raising of rate.By modifying phosphoric acid on graphene oxide, phosphate radical can reduce dependence of the proton conduction property to water content, by force
Change the water retention property of film.Phosphorylation graphene oxide doped is entered to the hybridized film prepared in film, both proton conduction with higher
Rate, and good water holding capacity can be kept, remain to that there is ideal proton conductivity under high temperature low humidity.To being at present
Only, Nafion/ phosphorylation graphene oxide hybridized film has no document report for fuel battery proton exchange film.
Summary of the invention
It is an object of that present invention to provide a kind of Nafion/ phosphorylation graphene oxide hybridized film and its preparations and application.It should
Hybridized film is used for Proton Exchange Membrane Fuel Cells, there is higher proton conductivity under 100% humidity and low humidity, prepares
Method is simple.
In order to solve the above-mentioned technical problem, a kind of Nafion/ phosphorylation graphene oxide hybridized film proposed by the present invention, by
Nafion and phosphorylation graphene oxide are constituted, and hybridized film is with a thickness of 40~70 μm, wherein phosphorylation graphene oxide with
Nafion mass ratio is 0.005~0.02:1.
The preparation method of above-mentioned Nafion/ phosphorylation graphene oxide hybridized film, comprising the following steps:
Step 1: Hummers method prepares graphene oxide；
Step 2: the preparation of phosphorylation graphene oxide: trishydroxymethylaminomethane being dissolved in deionized water and is configured to
Concentration is 0.01mol L-1Buffer solution, add graphene oxide into the buffer solution, wherein graphene oxide concentration is
Dopamine is added into solution according to the amount of graphene oxide and dopamine 1:1 by 0.1~1.0mg/mL, sufficiently ultrasound, stirring,
Continue ultrasonic disperse；Above-mentioned reaction solution is transferred in three-necked flask, is placed in 30 DEG C of waters bath with thermostatic control and stirs for 24 hours, be centrifuged, wash
It washs, obtains the amine-modified graphene oxide of DOPA；Alendronic acid is weighed, is slowly added into above-mentioned reaction solution, the mixed solution
The concentration of middle alendronic acid is 0.1~0.8mg/mL, and after being stirred to react for 24 hours, centrifugation, washing, freeze-drying obtain phosphorylation oxygen
Graphite alkene；
Step 3: the preparation and film forming of hybridized film: Nafion solution being placed in drying in baking oven and for 24 hours, obtains drying
Nafion macromolecule；It weighs appropriate phosphorylation graphene oxide to be added in n,N-dimethylacetamide, stirring for 24 hours, is configured to dense
Degree is the mixed solution of 0.05~0.20g/mL；Dry Nafion macromolecule is dissolved in above-mentioned mixed solution, wherein
Nafion concentration is 0.02~0.1g/mL, and stirring to abundant dissolution, obtains casting solution for 24 hours；Casting solution is prolonged and flows to clean glass
In glass plate, it is placed in 80 DEG C of baking ovens dry 12h, 120 DEG C is warming up to and continues after drying 12h, obtained hybridized film is taken off, that is, is made
Obtain Nafion/ phosphorylation graphene oxide hybridized film, wherein phosphorylation graphene oxide is 0.005 with Nafion mass ratio
~0.02:1.
Nafion/ phosphorylation graphene oxide hybridized film obtained above is used as fuel battery proton exchange film, in temperature
Under 110 DEG C of degree, 100% humidity, proton conductivity is 0.124~0.293S cm-1；Under 80 DEG C of temperature, 40% humidity, proton
Conductivity is 0.00581~0.0441S cm-1。
Compared with the prior art, the present invention has the advantages that
The fixation that phosphate group is realized using graphene oxide two-dimensional material as carrier, prepares oxygen by Hummers method first
Graphite alkene；Surface of graphene oxide is acted on followed by the autohemagglutination of dopamine and wraps up a strata dopamine, then by poly- more
Michael addition reaction bar between amine and amino, by the alendronic acid with amino by stable covalent supporting to aoxidizing stone
On black alkene lamella, the fixation of phosphate group is realized；Finally phosphorylation graphene oxide doped obtained is entered in Nafion membrane, is made
Obtain Nafion/ phosphorylation graphene oxide hybridized film.The preparation step of hybridized film of the present invention is environmentally protective, simple controllable, oxidation
The laminated structure of graphene constructs novel proton transfer channel in film, improves the proton conductivity of hybridized film, in temperature 110
DEG C, proton conductivity reaches 0.124~0.293S cm under 100% humidity-1.In addition, the introducing of phosphate group enhances the guarantor of film
Outlet capacity solves the problems, such as proton exchange membrane proton conductivity rapid drawdown under the low humidity, shows under low humidity/water-less environment
Good proton conductivity out, proton conductivity reaches 0.00581~0.0441Scm under 80 DEG C of temperature, 40% humidity-1。
Detailed description of the invention
Fig. 1 is the section SEM figure of pure Nafion membrane made from comparative example 1；
Fig. 2 is the section SEM figure of Nafion/PGO-0.5 hybridized film made from embodiment 1, wherein Nafion/PGO-0.5
The mass ratio for indicating phosphorylation graphene oxide PGO and Nafion is 0.005:1；
Fig. 3 is the section SEM figure of Nafion/PGO-1 hybridized film made from embodiment 2, wherein Nafion/PGO-1 is indicated
The mass ratio of phosphorylation graphene oxide PGO and Nafion are 0.01:1；
Fig. 4 is the section SEM figure of Nafion/PGO-1.5 hybridized film made from embodiment 3, wherein Nafion/PGO-1.5
The mass ratio for indicating phosphorylation graphene oxide PGO and Nafion is 0.015:1；
Fig. 5 is the section SEM figure of Nafion/PGO-2 hybridized film made from embodiment 4, wherein Nafion/PGO-2 is indicated
The mass ratio of phosphorylation graphene oxide PGO and Nafion are 0.02:1；
Fig. 6 is the Nafion/ phosphorylation graphene oxide hybridized film prepared under different phosphorylation graphene oxide loadings
Proton conductivity at different temperatures；
Fig. 7 is the Nafion/ phosphorylation graphene oxide hybridized film prepared under different phosphorylation graphene oxide loadings
Proton conductivity under 40% relative humidity.
Specific embodiment
Detailed process of the invention is told about by the following examples, and providing embodiment is the convenience for understanding, definitely not
The limitation present invention.
Comparative example 1: pure Nafion membrane is prepared.
Nafion solution is placed in drying in baking oven and for 24 hours, obtains dry Nafion macromolecule.Weigh 0.2g Nafion
3mLN is added in film, and in N- dimethyl acetamide (DMAc), stirring is for 24 hours to abundant dissolution to get arriving casting solution.Casting solution is prolonged into stream
Onto clean glass plate, it is placed in 80 DEG C of baking ovens after dry 12h and is warming up to 120 DEG C and continues dry 12h.Obtained film is taken off
Under, it can be prepared by pure Nafion membrane.Fig. 1 is the section SEM figure of pure Nafion membrane obtained, tests the film proton conductivity,
110 DEG C of temperature, proton conductivity is 0.124S cm under 100% humidity-1, proton conductivity is under 80 DEG C of temperature, 40% humidity
0.00581S cm-1。
Embodiment 1: preparation Nafion/PGO-0.5 hybridized film, steps are as follows:
Step 1: Hummers method prepares graphene oxide (GO): the 120mL concentrated sulfuric acid, 2g scale being added into round-bottomed flask
Graphite and 15g KMnO4, it is stirred to react 40min in 35 DEG C of waters bath with thermostatic control, deionized water dilute reaction solution is then used, then adds
Enter a certain amount of 5% H2O2, filter, centrifuge washing obtains GO after freeze-drying.The Hummers method prepares graphene oxide and belongs to
The art common knowledge.
Step 2: the preparation of phosphorylation graphene oxide (PGO): trishydroxymethylaminomethane (Tris) is dissolved in deionization
It is 0.01mol L that concentration is configured in water-1Buffer solution, GO made from step 1 is added in above-mentioned buffer solution, sufficiently
Ultrasound, stirring are added 30mg dopamine and continue ultrasonic disperse.Above-mentioned reaction solution is transferred in three-necked flask, 30 DEG C of perseverances are placed in
It is stirred in tepidarium for 24 hours, centrifugation, washing obtain the amine-modified graphene oxide of DOPA, be denoted as DGO.Weigh 40mg A Lun phosphine
Acid is slowly added into above-mentioned reaction solution, and after being stirred to react for 24 hours, centrifugation, washing, freeze-drying obtain phosphorylation graphite oxide
Alkene is denoted as PGO.
Step 3: the preparation and film forming of hybridized film: Nafion solution being placed in drying in baking oven and for 24 hours, obtains drying
Nafion macromolecule.3mLN is added in the PGO for weighing the preparation of 0.001g step 2, in N- dimethyl acetamide (DMAc), stirring
For 24 hours, it is sufficiently mixed PGO with DMAc.Then the dry Nafion of 0.2g being dissolved in above-mentioned solution, stirring is dissolved to abundant for 24 hours,
Obtain casting solution.Casting solution is prolonged and is flowed on clean glass plate, is warming up to 120 DEG C after being placed in 80 DEG C of baking ovens dry 12h
Continue dry 12h.Obtained hybridized film is taken off, can be prepared by Nafion/PGO-0.5 hybridized film.
The Nafion/ phosphorylation graphene oxide hybridized film that embodiment 1 is prepared, wherein phosphorylation graphene oxide
The mass ratio of PGO and Nafion is 0.005:1；Fig. 2 is that the section SEM of the hybridized film schemes, and You Tuzhong can be seen that PGO divides in film
It dissipates uniformly, Nafion macromolecule and PGO compatibility are good, the uniform zero defect of hybridized film.The proton conductivity of the hybridized film is tested,
Proton conductivity is 0.149S cm under 110 DEG C of temperature, 100% humidity-1, the proton conductivity under 80 DEG C of temperature, 40% humidity
For 0.0128S cm-1。
Embodiment 2: preparation Nafion/PGO-1 hybridized film, preparation process condition is substantially the same manner as Example 1, and difference is only
It is preparation and the film forming procedure of step 3 hybridized film, wherein the amount of weighed phosphorylation graphene oxide PGO is changed by 0.001g
For 0.002g, Nafion/PGO-1 hybridized film is finally made.
The Nafion/ phosphorylation graphene oxide hybridized film that embodiment 2 is prepared, wherein phosphorylation graphene oxide
The mass ratio of PGO and Nafion is 0.01:1.Fig. 3 is that the section SEM of the hybridized film schemes, and You Tuzhong can be seen that PGO divides in film
It dissipates uniformly, Nafion macromolecule and PGO compatibility are good, the uniform zero defect of hybridized film.The proton conductivity of the hybridized film is tested,
Proton conductivity is 0.184S cm under 110 DEG C of temperature, 100% humidity-1, the proton conductivity under 80 DEG C of temperature, 40% humidity
For 0.0196S cm-1。
Embodiment 3: preparation Nafion/PGO-1.5 hybridized film, preparation process condition is substantially the same manner as Example 1, different
It is only that preparation and the film forming procedure of step 3 hybridized film, wherein the amount of weighed PGO is changed to 0.003g by 0.001g, finally
Nafion/PGO-1.5 hybridized film is made.
The Nafion/ phosphorylation graphene oxide hybridized film that embodiment 3 is prepared, wherein phosphorylation graphene oxide
The mass ratio of PGO and Nafion is 0.015:1.Fig. 4 is that the section SEM of the hybridized film schemes, and You Tuzhong can be seen that PGO divides in film
It dissipates uniformly, Nafion macromolecule and PGO compatibility are good, the uniform zero defect of hybridized film.The proton conductivity of the hybridized film is tested,
Proton conductivity is 0.223S cm under 110 DEG C of temperature, 100% humidity-1, the proton conductivity under 80 DEG C of temperature, 40% humidity
For 0.0295S cm-1。
Embodiment 4: preparation Nafion/PGO-2 hybridized film, preparation process condition is substantially the same manner as Example 1, and difference is only
It is preparation and the film forming procedure of step 3 hybridized film, wherein the amount of weighed PGO is changed to 0.004g by 0.001g, final to make
Obtain Nafion/PGO-2 hybridized film.
The Nafion/ phosphorylation graphene oxide hybridized film that embodiment 4 is prepared, wherein phosphorylation graphene oxide
The mass ratio of PGO and Nafion is 0.02:1.Fig. 5 is that the section SEM of the hybridized film schemes, and You Tuzhong can be seen that PGO divides in film
It dissipates uniformly, Nafion macromolecule and PGO compatibility are good, the uniform zero defect of hybridized film.The proton conductivity of the hybridized film is tested,
Proton conductivity is 0.293S cm under 110 DEG C of temperature, 100% humidity-1, the proton conductivity under 80 DEG C of temperature, 40% humidity
For 0.0441S cm-1。
In conclusion the present invention is prepared for phosphorylation graphene oxide, and it is doped into film and is prepared for Nafion/ phosphorus
It is acidified graphene oxide hybridized film.By changing the loading of phosphorylation graphene oxide, to regulate and control phosphate group in hybridized film
Content and proton transfer channel quantity, to regulate and control the proton conduction property of proton exchange membrane.As shown in fig. 6, being doped into
After phosphorylation graphene oxide, the proton conductivity of hybridized film is significantly improved compared to pure film, as can be seen that phosphorus in Fig. 7
The introducing of acidification graphene oxide enhances the proton conductivity of hybridized film under the low humidity, and it is aobvious to improve degree compared to pure film
It writes.
Operation is simple for the preparation process of hybridized film of the present invention, environmentally protective, and Nafion/ phosphorylation obtained aoxidizes stone
Black alkene hybridized film is applied to Proton Exchange Membrane Fuel Cells, there is higher proton conductivity under 100% humidity and low humidity.
Although above in conjunction with figure, invention has been described, and the invention is not limited to above-mentioned specific embodiment parties
Formula, the above mentioned embodiment is only schematical, rather than restrictive, and those skilled in the art are in this hair
Under bright enlightenment, without deviating from the spirit of the invention, many variations can also be made, these belong to guarantor of the invention
Within shield.
Claims (2)
1. a kind of preparation method of Nafion/ phosphorylation graphene oxide hybridized film, the Nafion/ phosphorylation graphene oxide are miscellaneous
Change film to be made of Nafion and phosphorylation graphene oxide, hybridized film is with a thickness of 40~70 μm, wherein phosphorylation graphene oxide
It is 0.005~0.02:1 with Nafion mass ratio；It is characterized in that, the preparation method the following steps are included:
Step 1: Hummers method prepares graphene oxide；
Step 2: the preparation of phosphorylation graphene oxide:
Trishydroxymethylaminomethane is dissolved in deionized water and is configured to concentration as 0.01mol L-1Buffer solution, stone will be aoxidized
Black alkene is added in the buffer solution, and wherein graphene oxide concentration is 0.1~1.0mg/mL, sufficiently ultrasound, stirring, according to oxidation
Dopamine is added into solution for the amount of graphene and dopamine 1:1, continues ultrasonic disperse；Above-mentioned reaction solution is transferred to three mouthfuls of burnings
It in bottle, is placed in 30 DEG C of waters bath with thermostatic control and stirs for 24 hours, centrifugation, washing obtain the amine-modified graphene oxide of DOPA；
Alendronic acid is weighed, is slowly added into above-mentioned reaction solution and obtains mixed solution, alendronic acid is dense in the mixed solution
Degree is 0.1~0.8mg/mL, and after being stirred to react for 24 hours, centrifugation, washing, freeze-drying obtain phosphorylation graphene oxide；
Step 3: the preparation and film forming of hybridized film:
Nafion solution is placed in drying in baking oven and for 24 hours, obtains dry Nafion macromolecule；
Appropriate phosphorylation graphene oxide is weighed to be added in n,N-dimethylacetamide, stirring for 24 hours, be configured to concentration be 0.05~
The mixed solution of 0.20g/mL；Dry Nafion macromolecule is dissolved in above-mentioned mixed solution, wherein Nafion concentration is
0.02~0.1g/mL, stirring to abundant dissolution, obtain casting solution for 24 hours；Casting solution is prolonged and is flowed on clean glass plate, is placed in
Dry 12h in 80 DEG C of baking ovens is warming up to 120 DEG C and continues after drying 12h, obtained hybridized film is taken off, Nafion/ phosphorus is obtained
It is acidified graphene oxide hybridized film, wherein phosphorylation graphene oxide is 0.005~0.02:1 with Nafion mass ratio.
2. a kind of application of Nafion/ phosphorylation graphene oxide hybridized film, will be as made from claim 1 preparation method
Nafion/ phosphorylation graphene oxide hybridized film is used as fuel battery proton exchange film, under 110 DEG C of temperature, 100% humidity,
Proton conductivity is 0.124~0.293S cm-1；Under 80 DEG C of temperature, 40% humidity, proton conductivity be 0.00581~
0.0441S cm-1。
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| KR101825323B1 (en) * | 2017-02-17 | 2018-02-02 | 서울대학교산학협력단 | Ion-exchange membrane |
| CN108837799A (en) * | 2018-06-05 | 2018-11-20 | 中国科学院兰州化学物理研究所 | It is a kind of can Magnetic Isolation ferroso-ferric oxide/phosphorylation graphene composite nano material and its application |
| CN111318185B (en) * | 2018-12-17 | 2022-04-05 | 中国石油化工股份有限公司 | Coating process of graphene filter membrane material with enhanced hydrophilicity |
| CN110304624B (en) * | 2019-07-05 | 2023-03-21 | 郑州大学 | Carbon quantum dot functionalized graphene oxide laminated membrane and preparation and application thereof |
| CN111261914B (en) * | 2020-01-20 | 2023-06-09 | 青岛大学 | Graphene oxide polymer composite proton exchange membrane and preparation method and application thereof |
| CN114634642B (en) * | 2022-02-23 | 2023-03-10 | 华中科技大学 | PCNT (prestressed concrete) and PGO (PGO) synergistically modified polymer hybrid proton exchange membrane and preparation method thereof |
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